CN103773966A - Method for separating and utilizing neodymium iron boron waste materials - Google Patents
Method for separating and utilizing neodymium iron boron waste materials Download PDFInfo
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Abstract
The invention provides a method for separating and utilizing neodymium iron boron waste materials. The method comprises the following sequential steps of dissolution with hydrochloric acid, primary solid-liquid separation, precipitation with oxalic acid, secondary solid-liquid separation, hydrolysis process, third solid-liquid separation, acidic oxidation process, precipitation of ferric phosphate, fourth solid-liquid separation, evaporation and concentration, and fifth solid-liquid separation. Iron oxide red and praseodymium oxide are obtained through the steps of dissolution with hydrochloric acid, primary solid-liquid separation, precipitation with oxalic acid and secondary solid-liquid separation; iron oxide red and ferric phosphate precipitate are obtained through the steps of dissolution with hydrochloric acid, primary solid-liquid separation, precipitation with oxalic acid, secondary solid-liquid separation, hydrolysis process, third solid-liquid separation, acidic oxidation process, precipitation of ferric phosphate and fourth solid-liquid separation; ammonium chloride is obtained through the steps of dissolution with hydrochloric acid, primary solid-liquid separation, precipitation with oxalic acid, secondary solid-liquid separation, hydrolysis process, third solid-liquid separation, acidic oxidation process, precipitation of ferric phosphate, fourth solid-liquid separation, the evaporation and concentration and fifth solid-liquid separation. The method is high in recovery rate and purity, environment-friendly and pollution-free, low in recovery cost and the like.
Description
Technical field
The invention belongs to the technical field of rare earth resources recycling, specifically a kind of extraction and application method of neodymium iron boron waste material.
Background technology
Neodymium iron boron is rear earth element nd, Boron, praseodymium etc. and the alloy of ferric oxide, is a kind of permanent magnet material with high remanent magnetism, high-coercive force, high energy product, in modern industry and electronic technology, is applied widely.In the process of production Nd-Fe-B permanent magnetic element, because of the shape size of various elements different, the precision processing such as blank neodymium iron boron need to be cut, cuts, mill, in this precision processing process, will inevitably produce processing waste material, according to statistics, neodymium iron boron waste material accounts for 20% left and right of blank total amount, and this is for the huge neodymium iron boron of demand, and the neodymium iron boron waste material amount of generation is very huge.
Due to the composition of neodymium iron boron waste material and the composition of finished product Nd-Fe-Bo permanent magnet material basically identical, containing rare earth composition approximately 30%, iron approximately 60～65%; In approximately 30% rare earth composition, praseodymium is about 20～25%, neodymium is about 75～80%, and according to the performance difference of each element, each neodymium iron boron waste material also has the rare earth elements such as a small amount of dysprosium, terbium, Gadolinium, lanthanum, cerium, samarium.In order effectively to utilize rare earth resources, in industry, conventionally can carry out extraction and application processing to neodymium iron boron waste material, to extract rare earth element rare in neodymium iron boron waste material.
What traditional neodymium iron boron waste material extraction and application was processed main employing is the technological measures such as calcining, grinding.The problem of its existence is: 1. resource consumption is high, the rate of recovery is low, has significantly increased Separation and Recovery cost, extremely impracticable; 2. the rare earth element quality that Separation and Recovery obtains is lower, and industrially recycling can affect the performance quality of finished product Nd-Fe-Bo permanent magnet material; 3. extraction and application measure is imperfect, only separation and Extraction rare earth element, other material that neodymium iron boron waste material is contained, such as metallic compound (red iron oxide, tertiary iron phosphate), ammonium chloride etc., no longer separation and Extraction, directly discharge, has not only caused severe environmental pollution, and has further increased the Separation and Recovery cost of rare earth element.
In view of the problem of traditional neodymium iron boron waste material extraction and application technology existence, in recent years, the separation and recovery technology that has in succession occurred various novelties, uniqueness in industry, these technology are appeared in the newspapers repeatly on public publication, but occur so far there are no identical with content of the present invention or akin technology.
Summary of the invention
The object of the invention is to: for above-mentioned the deficiencies in the prior art, provide a kind of low in resources consumption, the rate of recovery is high, reclaim that purity is high, the extraction and application method of Separation and Recovery is complete, environment friendly and pollution-free, byproduct use value is high, Separation and Recovery cost is low, reliable and practical neodymium iron boron waste material.
The technical solution used in the present invention is that a kind of extraction and application method of neodymium iron boron waste material, comprises following order step:
A. dissolving with hydrochloric acid: adding concentration in neodymium iron boron waste material is that 15～25% hydrochloric acid carries out acidolysis, the pH value of acidolysis terminal is 1.5～2.5, and the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature >=90 ℃, the acidolysis time is 2～3 hours, and neodymium iron boron waste material is fully dissolved by hydrochloric acid;
B. a solid-liquid separation: the solution of steps A is carried out to solid-liquid separation, obtain filter residue one time, a filter residue is after the high-temperature calcination of 400～600 ℃, repeating step A, B, after repeating step A, B, obtain secondary filter residue, this secondary filter residue is red iron oxide, directly outer selling; The filtrate obtaining after solid-liquid separation enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 60～90 ℃, adds oxalic acid in filtrate, the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.1～1.2:1, at least reacted after 25 minutes, left standstill 3～4 hours;
D. two solid-liquid separation: the solution of step C is carried out to solid-liquid separation, and the solid matter obtaining is dried after washing, roasting, and maturing temperature is 850～1000 ℃, and roasting time is 2～4 hours, obtains purity and reaches more than 98% oxidation Praseodymium neodymium; After solid-liquid separation, obtain liquid phase substance and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.01～0.02:1, the pH value that makes solution is 5～7, be hydrolyzed, hydrolysis temperature is 90～95 ℃, hydrolysis time is 4～6 hours, and the metallic impurity beyond iron in solution are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out to solid-liquid separation, and the filter residue obtaining is repeating step A, B after the high-temperature calcination of 400～600 ℃, after repeating step A, B, obtaining secondary filter residue is red iron oxide, directly outer selling; The filtrate that solid-liquid separation obtains enters acid, oxidation operation;
G. acid, oxidation operation: adding concentration in the filtrate of step F is that 85% industrial phosphoric acid carries out acidifying, and in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5; In souring soln, add hydrogen peroxide to be oxidized, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.66～0.68:1, and oxidizing temperature is 40～60 ℃, and oxidization time is 40～60 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate to react in the oxidizing solution of step G, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.8～1.2:1, and temperature of reaction is 40～60 ℃, and the reaction times is 50～60 minutes; After question response completes, the pH value of reaction soln is adjusted to 1.5～2.5 with ammoniacal liquor, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained to product and carry out solid-liquid separation, the slurry that the filter cake furnishing concentration obtaining is 50%, under whipped state, in slurries, adding concentration is 85% industrial phosphoric acid, the mass ratio of industrial phosphoric acid and slurries is 0.04:1, the concentration that makes phosphoric acid in slurries is 0.5 mol/L, be warming up to 60～90 ℃, react 30～60 minutes, after question response completes, the pH value of reaction soln is adjusted to 2.5～3.5 with ammoniacal liquor, again reaction soln is filtered, the filter cake forming is dried after washing under the condition of 60～90 ℃, obtain ferrophosphorus than the battery-grade iron phosphate for 1:0.97～1.02, the filtrate that solid-liquid separation and washing, filtration obtain enters respectively evaporation concentration operation,
J. evaporation concentration: carry out evaporation concentration after twice filtrate of step I is mixed, make filtrate be evaporated to hypersaturated state, evaporation gas is condensed into after water, causes dissolving with hydrochloric acid and/or solid-liquid separation process; Supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution that step J is obtained is carried out centrifugation, obtains ammonium chloride, directly outer selling; The mother liquor that separation obtains is back to step J, and to carry out repeated evaporation concentrated.
Further, the hydrochloric acid in steps A is through deionized water or distilled water diluting and obtain by the technical hydrochloric acid of concentration 32%.
Further, the oxalic acid in step C is the industrial ethanedioic acid of content 99.6%.
Further, reduced iron powder iron level >=98% in step e.
Further, the hydrogen peroxide in step G is the industrial hydrogen peroxide of massfraction > 25%.
Further, the diammonium phosphate in step H is industrial phosphoric acid two ammoniums of content > 98%.
Further, the ammoniacal liquor in step H, I is the industrial ammonia of content > 25%.
Further, the separating device of a described solid-liquid separation, secondary solid-liquid separation, three solid-liquid separation, four solid-liquid separation employings is respectively plate-and-frame filter press.
The invention has the beneficial effects as follows: aforesaid method passes through dissolving with hydrochloric acid, oxalic acid precipitation, hydrolysis, a series of complete operations such as evaporation concentration, effectively, reliably Separation and Recovery rare in neodymium iron boron waste material, highly purified rare earth element-praseodymium neodymium, simultaneously Separation and Recovery the high metallic compound (red iron oxide of use value, tertiary iron phosphate) and byproduct ammonium chloride, turn waste into wealth, a large amount of consumption of neodymium iron boron waste material resource are avoided, waste and environmental pollution, significantly improve the rate of recovery, and then significantly reduce the Separation and Recovery cost of neodymium iron boron waste material, environment friendly and pollution-free, reliable and practical, manufacturing enterprise's economic benefit is high.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet of the present invention.
Embodiment
Referring to Fig. 1: below in conjunction with drawings and Examples, the present invention is further illustrated.
embodiment 1
The present invention includes following order step:
A. dissolving with hydrochloric acid: adding concentration in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) is that 20% hydrochloric acid carries out acidolysis, this hydrochloric acid is to be obtained through deionized water dilution by the technical hydrochloric acid of concentration 32%, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 95 ℃, the acidolysis time is 3 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 2;
B. a solid-liquid separation: the solution of steps A is carried out to solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 450 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, after repeating step A, B, obtain the secondary filter residue of about 138kg, this secondary filter residue is red iron oxide, uses deionized water wash 3 times, after pressing dry, directly outer selling, for building materials, coating etc.; The filtrate that obtains after solid-liquid separation (filter residue separates to separate with secondary filter residue and obtains) is the about 70g/L of total amount of rare earth, the about 3.4m of volume
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 80 ℃, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.14:1, and oxalic acid has added and has been about 271kg, react after 30 minutes, leave standstill 3 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 35 ℃, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (being praseodymium oxalate neodymium) obtaining, after deionized water wash 3 times, obtains the solid matter of about 582kg; By solid matter dry, roasting, maturing temperature is 900 ℃, roasting time is 3 hours, and praseodymium oxalate neodymium is fully oxidized, and obtains purity and reaches 99.12% the about 237kg of oxidation Praseodymium neodymium; After solid-liquid separation, obtain liquid phase substance and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.015:1, the add-on that is reduced iron powder is about 21kg, and intensification Accelerating reduction iron powder reacts with free acid, and the pH value that makes solution is 5, be hydrolyzed, hydrolysis temperature is 91 ℃, and hydrolysis time is 5 hours, and the metallic impurity beyond iron in solution are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out to solid-liquid separation by plate-and-frame filter press, the about 50kg(of filter residue obtaining is fully hydrolyzed because of other metallic impurity in solution, in the filter residue obtaining, the overwhelming majority is ironic hydroxide), these filter residues are through 450 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, after B, obtaining secondary filter residue is red iron oxide, with deionized water by red iron oxide washing 3 times, press dry rear directly outer selling, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, after the oxalic acid reaction that adds about 13kg, obtain purity reach 99.13% oxidation Praseodymium neodymium 10.5kg by step D, and so far, the rare earth reclaiming is altogether about 247.5kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: adding concentration in the filtrate of step F is that 85% industrial phosphoric acid carries out acidifying, and in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, should to control be 40 ℃ to the temperature of solution, prevent that decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.66:1, the add-on that is hydrogen peroxide is about 913kg, and oxidization time is 45 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate to react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammoniums of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.829:1, the add-on that is diammonium phosphate is about 1147kg, temperature of reaction is 40 ℃, and the reaction times is 60 minutes; After question response completes, the pH value of reaction soln is adjusted to 2.5 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained to product and carry out solid-liquid separation by plate-and-frame filter press, the slurry that the filter cake furnishing concentration obtaining is 50%, under whipped state, in slurries, adding concentration is 85% industrial phosphoric acid, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, make the concentration of phosphoric acid in slurries adjust to 0.5 mol/L, be warming up to 90 ℃, react 40 minutes, after question response completes, the pH value of reaction soln is adjusted to 3.5 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake forming washs 3 times again, through 75 ℃ of oven dry, obtain ferrophosphorus than approximately 2.03 tons of the battery-grade iron phosphates for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters respectively evaporation concentration operation,
J. evaporation concentration: carry out evaporation concentration after twice filtrate of step I is mixed, make filtrate be evaporated to hypersaturated state, in whole evaporating concentration process, under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure, carry out as far as possible, to prevent that ammonium chloride from decomposing, evaporation gas be condensed into after water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (approximately 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution that step J is obtained is carried out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, directly outer selling, for fertilizer and production of compound fertilizer etc.; The mother liquor (about 1.4m) that separation obtains is back to step J, and to carry out repeated evaporation concentrated, the discharge of having stopped ammonium nitrogen.
Filter residue in solid-liquid separation of the present invention and three solid-liquid separation process can together carry out high-temperature calcination.
embodiment 2
The present invention includes following order step:
A. dissolving with hydrochloric acid: adding concentration in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) is that 20% hydrochloric acid carries out acidolysis, this hydrochloric acid is to be obtained through deionized water dilution by the technical hydrochloric acid of concentration 32%, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 100 ℃, the acidolysis time is 2.5 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 1.8;
B. a solid-liquid separation: the solution of steps A is carried out to solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 550 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, after repeating step A, B, obtain the secondary filter residue of about 138kg, this secondary filter residue is red iron oxide, uses deionized water wash 3 times, after pressing dry, directly outer selling, for building materials, coating etc.; The filtrate that obtains after solid-liquid separation (filter residue separates to separate with secondary filter residue and obtains) is the about 70g/L of total amount of rare earth, the about 3.4m of volume
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 85 ℃, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.15:1, and oxalic acid has added and has been about 274kg, react after 35 minutes, leave standstill 3 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 30 ℃, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (being praseodymium oxalate neodymium) obtaining, after deionized water wash 3 times, obtains the solid matter of about 582kg; By solid matter dry, roasting, maturing temperature is 900 ℃, roasting time is 3 hours, and praseodymium oxalate neodymium is fully oxidized, and obtains purity and reaches 99.12% the about 237kg of oxidation Praseodymium neodymium; After solid-liquid separation, obtain liquid phase substance and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.016:1, the add-on that is reduced iron powder is about 22kg, and intensification Accelerating reduction iron powder reacts with free acid, and the pH value that makes solution is 5, be hydrolyzed, hydrolysis temperature is 95 ℃, and hydrolysis time is 5 hours, and the metallic impurity beyond iron in solution are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out to solid-liquid separation by plate-and-frame filter press, the about 50kg(of filter residue obtaining is fully hydrolyzed because of other metallic impurity in solution, in the filter residue obtaining, the overwhelming majority is ironic hydroxide), these filter residues are through 550 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, after B, obtaining secondary filter residue is red iron oxide, with deionized water by red iron oxide washing 3 times, press dry rear directly outer selling, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, after the oxalic acid reaction that adds about 13kg, obtain purity reach 99.13% oxidation Praseodymium neodymium 10.5kg by step D, and so far, the rare earth reclaiming is altogether about 247.5kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: adding concentration in the filtrate of step F is that 85% industrial phosphoric acid carries out acidifying, and in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, should to control be 45 ℃ to the temperature of solution, prevent that decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.665:1, the add-on that is hydrogen peroxide is about 920kg, and oxidization time is 45 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate to react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammoniums of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.85:1, the add-on that is diammonium phosphate is about 1176kg, temperature of reaction is 45 ℃, and the reaction times is 60 minutes; After question response completes, the pH value of reaction soln is adjusted to 2.5 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained to product and carry out solid-liquid separation by plate-and-frame filter press, the slurry that the filter cake furnishing concentration obtaining is 50%, under whipped state, in slurries, adding concentration is 85% industrial phosphoric acid, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, make the concentration of phosphoric acid in slurries adjust to 0.5 mol/L, be warming up to 90 ℃, react 45 minutes, after question response completes, the pH value of reaction soln is adjusted to 3.5 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake forming washs 3 times again, through 85 ℃ of oven dry, obtain ferrophosphorus than approximately 2.03 tons of the battery-grade iron phosphates for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters respectively evaporation concentration operation,
J. evaporation concentration: carry out evaporation concentration after twice filtrate of step I is mixed, make filtrate be evaporated to hypersaturated state, in whole evaporating concentration process, under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure, carry out as far as possible, to prevent that ammonium chloride from decomposing, evaporation gas be condensed into after water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (approximately 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution that step J is obtained is carried out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, directly outer selling, for fertilizer and production of compound fertilizer etc.; The mother liquor (about 1.4m) that separation obtains is back to step J, and to carry out repeated evaporation concentrated, the discharge of having stopped ammonium nitrogen.
Filter residue in solid-liquid separation of the present invention and three solid-liquid separation process can together carry out high-temperature calcination.
embodiment 3
The present invention includes following order step:
A. dissolving with hydrochloric acid: adding concentration in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) is that 23% hydrochloric acid carries out acidolysis, this hydrochloric acid is to be obtained through deionized water dilution by the technical hydrochloric acid of concentration 32%, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 105 ℃, the acidolysis time is 2.5 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 1.6;
B. a solid-liquid separation: the solution of steps A is carried out to solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 600 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, after repeating step A, B, obtain the secondary filter residue of about 138kg, this secondary filter residue is red iron oxide, uses deionized water wash 3 times, after pressing dry, directly outer selling, for building materials, coating etc.; The filtrate that obtains after solid-liquid separation (filter residue separates to separate with secondary filter residue and obtains) is the about 70g/L of total amount of rare earth, the about 3.4m of volume
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 90 ℃, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.17:1, and oxalic acid has added and has been about 278kg, react after 40 minutes, leave standstill 3.5 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 28 ℃, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (being praseodymium oxalate neodymium) obtaining, after deionized water wash 3 times, obtains the solid matter of about 582kg; By solid matter dry, roasting, maturing temperature is 980 ℃, roasting time is 3.5 hours, and praseodymium oxalate neodymium is fully oxidized, and obtains purity and reaches 99.12% the about 237kg of oxidation Praseodymium neodymium; After solid-liquid separation, obtain liquid phase substance and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.014:1, the add-on that is reduced iron powder is about 19.4kg, and intensification Accelerating reduction iron powder reacts with free acid, and the pH value that makes solution is 5.5, be hydrolyzed, hydrolysis temperature is 93 ℃, and hydrolysis time is 6 hours, and the metallic impurity beyond iron in solution are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out to solid-liquid separation by plate-and-frame filter press, the about 50kg(of filter residue obtaining is fully hydrolyzed because of other metallic impurity in solution, in the filter residue obtaining, the overwhelming majority is ironic hydroxide), these filter residues are through 600 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, after B, obtaining secondary filter residue is red iron oxide, with deionized water by red iron oxide washing 3 times, press dry rear directly outer selling, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, after the oxalic acid reaction that adds about 13.2kg, obtain purity reach 99.13% oxidation Praseodymium neodymium 10.5kg by step D, and so far, the rare earth reclaiming is altogether about 247.5kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: adding concentration in the filtrate of step F is that 85% industrial phosphoric acid carries out acidifying, and in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, should to control be 50 ℃ to the temperature of solution, prevent that decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.67:1, the add-on that is hydrogen peroxide is about 927kg, and oxidization time is 55 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate to react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammoniums of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 1:1, the add-on that is diammonium phosphate is about 1590kg, temperature of reaction is 55 ℃, and the reaction times is 50 minutes; After question response completes, the pH value of reaction soln is adjusted to 2.0 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained to product and carry out solid-liquid separation by plate-and-frame filter press, the slurry that the filter cake furnishing concentration obtaining is 50%, under whipped state, in slurries, adding concentration is 85% industrial phosphoric acid, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, make the concentration of phosphoric acid in slurries adjust to 0.5 mol/L, be warming up to 80 ℃, react 50 minutes, after question response completes, the pH value of reaction soln is adjusted to 3.0 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake forming washs 3 times again, through 90 ℃ of oven dry, obtain ferrophosphorus than approximately 2.03 tons of the battery-grade iron phosphates for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters respectively evaporation concentration operation,
J. evaporation concentration: carry out evaporation concentration after twice filtrate of step I is mixed, make filtrate be evaporated to hypersaturated state, in whole evaporating concentration process, under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure, carry out as far as possible, to prevent that ammonium chloride from decomposing, evaporation gas be condensed into after water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (approximately 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution that step J is obtained is carried out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, directly outer selling, for fertilizer and production of compound fertilizer etc.; The mother liquor (about 1.4m) that separation obtains is back to step J, and to carry out repeated evaporation concentrated, the discharge of having stopped ammonium nitrogen.
Filter residue in solid-liquid separation of the present invention and three solid-liquid separation process can together carry out high-temperature calcination.
embodiment 4
The present invention includes following order step:
A. dissolving with hydrochloric acid: adding concentration in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) is that 16% hydrochloric acid carries out acidolysis, this hydrochloric acid is to be obtained through deionized water dilution by the technical hydrochloric acid of concentration 32%, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 110 ℃, the acidolysis time is 3 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 2.5;
B. a solid-liquid separation: the solution of steps A is carried out to solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 500 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, after repeating step A, B, obtain the secondary filter residue of about 138kg, this secondary filter residue is red iron oxide, uses deionized water wash 3 times, after pressing dry, directly outer selling, for building materials, coating etc.; The filtrate that obtains after solid-liquid separation (filter residue separates to separate with secondary filter residue and obtains) is the about 70g/L of total amount of rare earth, the about 3.4m of volume
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 70 ℃, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.18:1, and oxalic acid has added and has been about 280kg, react after 40 minutes, leave standstill 4 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 25 ℃, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (being praseodymium oxalate neodymium) obtaining, after deionized water wash 3 times, obtains the solid matter of about 583kg; By solid matter dry, roasting, maturing temperature is 950 ℃, roasting time is 2.5 hours, and praseodymium oxalate neodymium is fully oxidized, and obtains purity and reaches 99.12% the about 237kg of oxidation Praseodymium neodymium; After solid-liquid separation, obtain liquid phase substance and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.018:1, the add-on that is reduced iron powder is about 25kg, and intensification Accelerating reduction iron powder reacts with free acid, and the pH value that makes solution is 6, be hydrolyzed, hydrolysis temperature is 95 ℃, and hydrolysis time is 4.5 hours, and the metallic impurity beyond iron in solution are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out to solid-liquid separation by plate-and-frame filter press, the about 50kg(of filter residue obtaining is fully hydrolyzed because of other metallic impurity in solution, in the filter residue obtaining, the overwhelming majority is ironic hydroxide), these filter residues are through 500 ℃ of high-temperature calcinations, filter residue is fully oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, after B, obtaining secondary filter residue is red iron oxide, with deionized water by red iron oxide washing 3 times, press dry rear directly outer selling, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, after the oxalic acid reaction that adds about 13.3kg, obtain purity reach 99.13% oxidation Praseodymium neodymium 11kg by step D, and so far, the rare earth reclaiming is altogether about 248kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: adding concentration in the filtrate of step F is that 85% industrial phosphoric acid carries out acidifying, and in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, should to control be 55 ℃ to the temperature of solution, prevent that decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.68:1, the add-on that is hydrogen peroxide is about 940kg, and oxidization time is 50 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate to react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammoniums of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.9:1, the add-on that is diammonium phosphate is about 1245kg, temperature of reaction is 55 ℃, and the reaction times is 55 minutes; After question response completes, the pH value of reaction soln is adjusted to 1.8 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained to product and carry out solid-liquid separation by plate-and-frame filter press, the slurry that the filter cake furnishing concentration obtaining is 50%, under whipped state, in slurries, adding concentration is 85% industrial phosphoric acid, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, make the concentration of phosphoric acid in slurries adjust to 0.5 mol/L, be warming up to 70 ℃, react 60 minutes, after question response completes, the pH value of reaction soln is adjusted to 2.5 with ammoniacal liquor, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake forming washs 3 times again, through 90 ℃ of oven dry, obtain ferrophosphorus than approximately 2.03 tons of the battery-grade iron phosphates for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters respectively evaporation concentration operation,
J. evaporation concentration: carry out evaporation concentration after twice filtrate of step I is mixed, make filtrate be evaporated to hypersaturated state, in whole evaporating concentration process, under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure, carry out as far as possible, to prevent that ammonium chloride from decomposing, evaporation gas be condensed into after water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (approximately 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution that step J is obtained is carried out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, directly outer selling, for fertilizer and production of compound fertilizer etc.; The mother liquor (about 1.4m) that separation obtains is back to step J, and to carry out repeated evaporation concentrated, the discharge of having stopped ammonium nitrogen.
Filter residue in solid-liquid separation of the present invention and three solid-liquid separation process can together carry out high-temperature calcination.
Claims (8)
1. an extraction and application method for neodymium iron boron waste material, comprises following order step:
A. dissolving with hydrochloric acid: adding concentration in neodymium iron boron waste material is that 15～25% hydrochloric acid carries out acidolysis, the pH value of acidolysis terminal is 1.5～2.5, and the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature >=90 ℃, the acidolysis time is 2～3 hours, and neodymium iron boron waste material is fully dissolved by hydrochloric acid;
B. a solid-liquid separation: the solution of steps A is carried out to solid-liquid separation, obtain filter residue one time, a filter residue is after the high-temperature calcination of 400～600 ℃, repeating step A, B, after repeating step A, B, obtain secondary filter residue, this secondary filter residue is red iron oxide, directly outer selling; The filtrate obtaining after solid-liquid separation enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 60～90 ℃, adds oxalic acid in filtrate, the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.1～1.2:1, at least reacted after 25 minutes, left standstill 3～4 hours;
D. two solid-liquid separation: the solution of step C is carried out to solid-liquid separation, and the solid matter obtaining is dried after washing, roasting, and maturing temperature is 850～1000 ℃, and roasting time is 2～4 hours, obtains purity and reaches more than 98% oxidation Praseodymium neodymium; After solid-liquid separation, obtain liquid phase substance and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.01～0.02:1, the pH value that makes solution is 5～7, be hydrolyzed, hydrolysis temperature is 90～95 ℃, hydrolysis time is 4～6 hours, and the metallic impurity beyond iron in solution are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out to solid-liquid separation, and the filter residue obtaining is repeating step A, B after the high-temperature calcination of 400～600 ℃, after repeating step A, B, obtaining secondary filter residue is red iron oxide, directly outer selling; The filtrate that solid-liquid separation obtains enters acid, oxidation operation;
G. acid, oxidation operation: adding concentration in the filtrate of step F is that 85% industrial phosphoric acid carries out acidifying, and in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5; In souring soln, add hydrogen peroxide to be oxidized, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.66～0.68:1, and oxidizing temperature is 40～60 ℃, and oxidization time is 40～60 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate to react in the oxidizing solution of step G, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.8～1.2:1, and temperature of reaction is 40～60 ℃, and the reaction times is 50～60 minutes; After question response completes, the pH value of reaction soln is adjusted to 1.5～2.5 with ammoniacal liquor, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained to product and carry out solid-liquid separation, the slurry that the filter cake furnishing concentration obtaining is 50%, under whipped state, in slurries, adding concentration is 85% industrial phosphoric acid, the mass ratio of industrial phosphoric acid and slurries is 0.04:1, the concentration that makes phosphoric acid in slurries is 0.5 mol/L, be warming up to 60～90 ℃, react 30～60 minutes, after question response completes, the pH value of reaction soln is adjusted to 2.5～3.5 with ammoniacal liquor, again reaction soln is filtered, the filter cake forming is dried after washing under the condition of 60～90 ℃, obtain ferrophosphorus than the battery-grade iron phosphate for 1:0.97～1.02, the filtrate that solid-liquid separation and washing, filtration obtain enters respectively evaporation concentration operation,
J. evaporation concentration: carry out evaporation concentration after twice filtrate of step I is mixed, make filtrate be evaporated to hypersaturated state, evaporation gas is condensed into after water, causes dissolving with hydrochloric acid and/or solid-liquid separation process; Supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution that step J is obtained is carried out centrifugation, obtains ammonium chloride, directly outer selling; The mother liquor that separation obtains is back to step J, and to carry out repeated evaporation concentrated.
2. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the hydrochloric acid in steps A is through deionized water or distilled water diluting and obtain by the technical hydrochloric acid of concentration 32%.
3. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the oxalic acid in step C is the industrial ethanedioic acid of content 99.6%.
4. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: reduced iron powder iron level >=98% in step e.
5. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the hydrogen peroxide in step G is the industrial hydrogen peroxide of massfraction > 25%.
6. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the diammonium phosphate in step H is industrial phosphoric acid two ammoniums of content > 98%.
7. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the ammoniacal liquor in step H, I is the industrial ammonia of content > 25%.
8. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the separating device that a described solid-liquid separation, secondary solid-liquid separation, three solid-liquid separation, four solid-liquid separation adopt is respectively plate-and-frame filter press.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058232A (en) * | 1990-07-19 | 1992-01-29 | 中南工业大学 | From neodymium iron boron waste material, extract the method for neodymium |
| CN1693493A (en) * | 2005-05-08 | 2005-11-09 | 西安西骏新材料有限公司 | Recovery method of valuable element in neodymium iron boron waste material |
| CN102206755A (en) * | 2011-03-06 | 2011-10-05 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
-
2014
- 2014-03-03 CN CN201410073670.6A patent/CN103773966B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058232A (en) * | 1990-07-19 | 1992-01-29 | 中南工业大学 | From neodymium iron boron waste material, extract the method for neodymium |
| CN1693493A (en) * | 2005-05-08 | 2005-11-09 | 西安西骏新材料有限公司 | Recovery method of valuable element in neodymium iron boron waste material |
| CN102206755A (en) * | 2011-03-06 | 2011-10-05 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
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